Life cycle analysis of grapeseed oil biofuel in Spain

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(1)UNIVERSIDAD POLITÉCNICA DE MADRID SCHOOL OF MINES AND ENERGY. Degree: MSc. in MINING ENGINEERING. MASTER THESIS PROJECT. DEPARTMENT OF ENERGY AND FUELS. LIFE CYCLE ANALYSIS OF GRAPESEED OIL BIOFUEL IN SPAIN. MARINA FERNÁNDEZ BARAJAS. FEBRUARY 2018.

(2) UNIVERSIDAD POLITÉCNICA DE MADRID SCHOOL OF MINES AND ENERGY. Degree: MSc. in MINING ENGINEERING. LIFE CYCLE ANALYSIS OF GRAPESEED OIL BIOFUEL IN SPAIN. AUTHOR: MARINA FERNÁNDEZ BARAJAS CO-DIRECTED BY: DAVID BOLONIO MARTÍN MARÍA JESÚS GARCÍA MARTÍNEZ. DEPARTMENT OF ENERGY AND FUELS. Signature of the Professor:. Date:.

(3) UNIVERSIDAD POLITÉCNICA DE MADRID SCHOOL OF MINES AND ENERGY. Degree: MSc. in MINING ENGINEERING. LIFE CYCLE ANALYSIS OF GRAPESEED OIL BIOFUEL IN SPAIN. Author MARINA FERNÁNDEZ BARAJAS. Co-directed by DAVID BOLONIO MARTÍN And MARÍA JESÚS GARCÍA MARTÍNEZ.

(4) ACKNOWLEDGEMENTS I would like to thank everyone who helped me complete this project, particularly to: Mr. David Bolonio Martín and Dr. María Jesús García Martínez, tutors of this project, for their constant help, patience, and guidance. To my friends, especially my WG-girls and Maria, who have become my German family and always have a positive point of view. And to my family and Javier, who always encourage and support me and advise me wisely..

(5) TABLE OF CONTENTS FIGURE INDEX ................................................................................................................................iv TABLE INDEX ..................................................................................................................................vi ABSTRACT .................................................................................................................................... viii RESUMEN .................................................................................................................................... viii. DOCUMENT 1: REPORT. 1. PURPOSE AND SCOPE ................................................................................................................ 2 2. INTRODUCTION ......................................................................................................................... 5 2.1 ENERGY AND BIOFUELS ....................................................................................................... 5 2.1.1 MAIN REASONS TO DEVELOP ALTERNATIVE FUELS. 5. 2.1.2 SUSTAINABLE DEVELOPMENT. 9. 2.2 WINE AND GRAPESEED OIL PRODUCTION ........................................................................ 11 2.2.1 WINE PRODUCTION IN SPAIN AND THE EUROPEAN UNION. 11. 2.2.2 WINEMAKING. 16. 2.2.3 GRAPESEED OIL PRODUCTION. 19. 2.3. BIODIESEL ......................................................................................................................... 21 2.3.1 CLASSIFICATION OF BIODIESEL. 21. 2.3.2 PRODUCTION OF BIODIESEL. 22. 2.3.3 ADVANTAGES AND DISADVANTAGES OF BIODIESEL. 29. 2.3.4 PROPERTIES OF BIODIESEL. 31. 2.4. LIFE CYCLE ASSESSMENT .................................................................................................. 33 2.4.1. APPLICATIONS OF THE LCA. 33. 2.4.2 REGULATION OF LCA. 36. 2.4.3 PRODUCT LIFE-CYCLE. 36. 2.4.4 THE DATA AND ITS RELIABILITY. 38. 2.4.5 THEORETICAL BASIS. 40. 3. METHODOLOGY ...................................................................................................................... 48 3. FAEE FROM GRAPESEED OIL................................................................................................ 48. i.

(6) 3.2 APPLICATION OF THE LCA TO THE CASE OF STUDY: GOAL AND SCOPE ............................ 48 3.2.1 DEFINITION OF THE FUNCTIONAL UNIT. 48. 3.2.2 STUDIED SYSTEMS. 49. 3.2.3 SYSTEM BOUNDARIES. 50. 3.2.4 ALLOCATION METHODS. 53. 3.2.5 PREVIOUS CONSIDERATIONS. 54. 3.3 LIFECYCLE INVENTORY (LCI) .............................................................................................. 56 3.3.1 BIOETHANOL PRODUCTION SYSTEM. 56. 3.3.2 GRAPESEED OIL PRODUCTION SYSTEM. 63. 3.3.3 TRANSESTERIFICATION SYSTEM. 64. 3.4 SELECTION OF THE IMPACT METHODOLOGY ................................................................... 66 4. RESULTS AND INTERPRETATION ............................................................................................. 68 4.1 CLIMATE CHANGE EMISSIONS ANALYSIS .......................................................................... 68 4.1.1 ANALYSIS OF GRAPESEED OIL AND FERMENTATION PROCESSES. 69. 4.1.2 ANALYSIS OF THE HARVEST PROCESS. 72. 4.1.3 ANALYSIS OF THE REMAINING PROCESSES. 74. 4.1.4 CONCLUSIONS ON THE ANALYSIS OF THE GHG EMISSIONS. 76. 4.2 LAND USE ANALYSIS .......................................................................................................... 76 4.3 WATER RESOURCE DEPLETION ANALYSIS ......................................................................... 76 4.4 COMPARISON WITH FAME FROM GRAPESEED OIL........................................................... 77 4.4.1 CLIMATE CHANGE EMISSIONS ANALYSIS. 79. 4.5 COMPARISON WITH PALM OIL BIODIESEL ........................................................................ 80 5. CONCLUSIONS ......................................................................................................................... 82 6. BIBLIOGRAPHY......................................................................................................................... 84. DOCUMENT 2: ECONOMIC STUDY. 1. COSTS OF THE PROJECT ........................................................................................................... 90 2. INCOMES OF THE PROJECT...................................................................................................... 93. ii.

(7) DOCUMENT 3: APPENDICES. 1. FLOWCHARTS OF THE PROCESSES .......................................................................................... 95 1.1 BIOETHANOL PRODUCION PROCESS ................................................................................. 95 1.1.1 GRAPE GROWING AND HARVESTING. 95. 1.1.2 FERMENTATION PROCESS. 97. 1.1.3 DISTILLATION PROCESS. 100. 1.2 GRAPESEED OIL PRODUCION PROCESS ........................................................................... 105 1.3 TRANSESTERIFICATION PROCESS FAEE ........................................................................... 106 1.4 TRANSESTERIFICATION PROCESS FAME .......................................................................... 107. iii.

(8) FIGURE INDEX Figure 1: Flowchart of the process ................................................................................................ 3 Figure 2: Total world energy consumption by source................................................................... 5 Figure 3: World energy consumption by source, 1990-2040 expressed in quadrillion British Thermal unit (Btu) ......................................................................................................................... 6 Figure 4: Global energy demand by sector expressed in billion tons of oil equivalent (toe) ....... 7 Figure 5: EU Oil Importers 2014: The top then by market share .................................................. 7 Figure 6: Plot of global temperature and CO2 concentration from 1880-2010. .......................... 8 Figure 7: Schematic representation of a generic life cycle of a product..................................... 10 Figure 8: Destemmer................................................................................................................... 17 Figure 9: Common extraction process of grapeseed oil ............................................................. 21 Figure 10: Regional production of ethanol and biodiesel in 2011 as a percentage of global production ................................................................................................................................... 23 Figure 11: Ethanol production in the USA ................................................................................... 24 Figure 12: Conversion processes of biofuels ............................................................................... 25 Figure 13: Production process of biodiesel ................................................................................. 26 Figure 14: Transesterification reaction of a vegetable oil with an alcohol ................................. 27 Figure 15: Possible pathways for bioethanol fermentation from cellulosic feedstock .............. 28 Figure 16: Product lifecycle, including disposal recycling ........................................................... 37 Figure 17: The basic structure of Ecoinvent database system .................................................... 40 Figure 18: Phases and applications of a LCA ............................................................................... 41 Figure 19: Four common options for defining system boundaries in LCA .................................. 42 Figure 20: Schema of a general Life Cycle Inventory .................................................................. 43 Figure 21: Elements of LCA ......................................................................................................... 44 Figure 22: Biofuels plants where distillation of the must could be performed .......................... 51 Figure 23: Biofuels plants where transesterification of the oil with the ethanol could be performed ................................................................................................................................... 52 Figure 24: Flowchart of the process referred to 1MJ of FAEE .................................................... 67 Figure 25: Contributions to the impact categories by processes and products ......................... 70 Figure 26: Flowchart for the grapeseed oil production process referred to 1 MJ of FAEE ......... 71 Figure 27: Flowchart for the fermentation process referred to 1 MJ of FAEE ........................... 71 Figure 28: Contributions of the processes plotted as single score by impact categories ........... 73 Figure 29: Flowchart for the harvest process referred to 1 MJ of FAEE ..................................... 74 Figure 30: Flowchart for the steam production process referred to 1 MJ of FAEE .................... 75 iv.

(9) Figure 31: Flowchart for the distillation process referred to 1 MJ of FAEE ................................ 75 Figure 32: Flowchart for the transesterification process referred to 1 MJ of FAEE.................... 75 Figure 33: Comparison between the three analyzed biodiesels .... ¡Error! Marcador no definido.. v.

(10) TABLE INDEX Table 1: Area currently planted with vineyards in Spain, detailed by regions............................ 12 Table 2: Area currently planted with vineyards in the EU, detailed by country ......................... 13 Table 3: Biodiesel global production from 2004 to 2015 ............................................................ 22 Table 4: EU Biodiesel Consumption (Million liters) ..................................................................... 25 Table 5: Legal definition of biodiesel according to EN 590:2004 and EN 14214:2012 ............... 31 Table 6: FAEE profiles .................................................................................................................. 49 Table 7: Allocation percentage (%) of emissions at different steps of the ethanol production . 53 Table 8: Inventory for grape harvesting, inputs ......................................................................... 57 Table 9: Inventory for grape harvesting, emissions .................................................................... 58 Table 10: Inventory for fermentation, outputs ........................................................................... 59 Table 11: Inventory for fermentation, inputs ............................................................................. 60 Table 12: Inventory for fermentation, emissions........................................................................ 60 Table 13: Inventory for distillation, outputs ............................................................................... 62 Table 14: Inventory for distillation, inputs .................................................................................. 62 Table 15: Inventory for grapeseed oil production, outputs ........................................................ 64 Table 16: Inventory for grapeseed oil production, inputs .......................................................... 64 Table 17: Inventory for FAEE transesterification, outputs .......................................................... 65 Table 18: Inventory of FAEE transesterification, inputs .............................................................. 65 Table 19: Results of the ILCD Analysis for 1 MJ of the grapeseed oil biofuel ............................. 68 Table 20: Results of the ILCD Analysis for the impact category 'Climate change' for 1 kg of the product 'seeds' from the fermentation process ......................................................................... 72 Table 21: Results of the ILCD Analysis for the impact category 'Climate change' for 1 kg of the product 'grape' from the harvest process................................................................................... 74 Table 22: Results of the ILCD Analysis for the impact category ‘Water resource depletion’ for 1 kg of the product 'grape' from the harvest process.................................................................... 77 Table 23: Inventory for FAME transesterification, outputs ........................................................ 77 Table 24: Inventory of FAME transesterification, inputs ............................................................ 78 Table 25: Results of the ILCD Analysis for 1 MJ of the grapeseed oil FAME ............................... 79 Table 26: Results of the ILCD Analysis of palm oil biofuel .......................................................... 80 Table 27: Densities used.............................................................................................................. 90 Table 28: Grape harvest costs ..................................................................................................... 90 Table 29: Fermentation costs ...................................................................................................... 91 Table 30: Distillation costs .......................................................................................................... 91 vi.

(11) Table 31: Grapeseed oil production ............................................................................................ 91 Table 32: Transesterification costs.............................................................................................. 91 Table 33: Total costs.................................................................................................................... 92 Table 34: Incomes ....................................................................................................................... 93. vii.

(12) ABSTRACT All the processes that are needed to provide our society with goods and services contribute to a wide range of environmental impacts. These emissions, generation of waste and consumption of resources occur at many stages in a product’s life cycle and they should be taken into account when analyzing it. In order to account and categorize them, life cycle analysis (LCAs) are carried out. In this project, the LCA of a biofuel, fatty acid ethyl esters (FAEE) from grapeseed oil, has been performed. Grapeseed oil can be considered as a waste, due to its minor consumption, and the ethanol used during the transesterification to produce the biofuel has a biological origin since wine surpluses and pomace have been distilled to produce it. The results of the LCA have been compared with the ones of fatty acid methyl esters (FAME) from grapeseed oil, where the methanol has a fossil origin, as well as with the ones from a palm oil FAME. An economic study has also been performed to prove that the analyzed FAEE not only meets stablished environmental criteria, but it is also economically profitable.. RESUMEN Todos los procesos necesarios para proveer a nuestra sociedad de bienes y servicios contribuyen en amplia medida a los impactos medioambientales. Las emisiones que se producen, la generación de residuos y el consumo de los recursos ocurren en todas las etapas del ciclo de vida del producto y deben ser tenidas en cuenta a la hora de analizarlo. Para ello, se llevan a cabo análisis del ciclo de vida (ACV). En este proyecto, se ha llevado a cabo un ACV de ésteres etílicos de ácidos grasos (FAEE) a partir de aceite de pepita de uva. Este aceite se pude considerar un residuo debido su bajo consumo, además el etanol usado en la transesterificación para producir el biodiesel tiene un origen biológico, ya que se ha destilado a partir de restos de vino y de hollejos. Los resultados del ACV se han comparado con los del ACV de ésteres metílicos de ácidos grasos (FAME) formados a partir de aceite de uva (en el que se usa metanol de origen fósil) y con los resultados del análisis de un FAME de aceite de palma. Además, se ha llevado a cabo un estudio económico para determinar que el FAEE analizado no sólo cumple con los criterios medioambientales establecidos, sino que también es económicamente rentable.. viii.

(13) LIFE CYCLE ANALYSIS OF GRAPESEED OIL BIOFUEL IN SPAIN. DOCUMENT 1: REPORT.

(14) 2. 1. PURPOSE AND SCOPE Sustainable development requires methods and tools to measure and compare the environmental impacts of human activities for the provision of goods and services. The life cycle assessment (LCA) is a methodological framework for estimating and assessing the environmental impacts attributable to the life cycle of a product, such as climate change, stratospheric ozone depletion, tropospheric ozone (smog) creation, eutrophication, acidification, toxicological stress on human health and ecosystems, noise, the depletion of resources and the use of water and land, among others. Renewable energies, such as biofuels, may be a solution for the constant growing energy demand. The general opinion about renewable energies is positive, due to the ‘renewable’ and ‘green’ aspects that are automatically associated with them. However, a LCA should be performed in every case to assure the real impacts of the analyzed energy. With this method, all the inputs and energy consumptions are taken into account and a comparison with other types of energies is feasible. Regarding the European legislation (European Commission, 2009), the greenhouse gas (GHG) emission saving from the use of biofuels and bioliquids shall be at least 50 %, being 60 % for biofuels and bioliquids produced in installations in which production started on or after 1 January 2017. For the calculation of the GHG emission saving, the following formula is used: SAVING = (EF – EB)/EF, where EB = total emissions from the biofuel or bioliquid; and EF = total emissions from the fossil fuel comparator, which is usually 83.8 g CO2 eq/MJ. This project has measured the impacts of biodiesel made of fatty acid ethyl esters (FAEE) produced from produced from grapeseed oil and wine surplus through a LCA. On one hand, grapeseed oil is hardly used and can be considered a waste, defining wastes as secondary products with little or no economic value, understanding secondary products as products of a process that have inelastic supply with demand where even if the market value of a secondary product increases one would not expect more of it to be produced from that process (ICF International, 2015). On the other hand, biodiesel is currently made using methanol, creating fatty acid methyl esters (FAME), which has a.

(15) 3. fossil origin, but, in this project, methanol is replaced by ethanol, obtained from the surplus of wine making and therefore producing a fully renewable biofuel. The wine production in Spain is limited by the European Union (EU) and therefore a lot of wine surpluses are left over each year in our country. These surpluses are normally eliminated through distillation to use it in the industry, as regarded in the European Community legislation, but could be used to produce biofuels. In contrast with energy produced from fossil resources, bioenergy from wine rests is sustainable in the long term. Therefore, it would be interesting to develop realistic and scalable technologies that are able to capture the energy in them and use it in the transportation sector as fuels. The simplified flowchart of the process, which will be carefully explained throughout the project, can be seen in Figure 1. The processes (harvest, fermentation, distillation, grapeseed oil production, transesterification, transport and steam production), as well as the final products for sale (FAEE, bioethanol, wine, biomass and grape liquor) can be seen in the flowchart.. Figure 1: Flowchart of the process. The whole process of production of the biofuel has been taking into account, including the winemaking process, the grapeseed oil extraction, and the transesterification process.

(16) 4. to obtain the biodiesel. Moreover, the results have been compared with the ones from a LCA of FAME from grapeseed oil (to see the influence of using a bio-ethanol instead of methanol) and the ones of a palm biodiesel. Palm biodiesel, currently the most used in Spain (Renewable Energy Magazine, 2014), is imported from Indonesia, which makes its transport emissions much higher than the biofuel that is being presented here, produced directly in Spain..

(17) 5. 2. INTRODUCTION 2.1 ENERGY AND BIOFUELS The increasing energy demand, the aim to reduce greenhouse gas (GHG) emissions, and the dependence on foreign fuel sources has motivated a development in the fuel industry. The research is going nowadays in direction of renewable fuels in order to make them as technically useful and economically competitive as fossil fuels. These new alternative fuels have to be really renewable, assessed by an exhaustive life cycle assessment (LCA). This tool makes feasible a further comparison between traditional fossil fuels and the new fuel. 2.1.1 MAIN REASONS TO DEVELOP ALTERNATIVE FUELS The development and use of renewable energy sources is a hot topic worldwide and both industry and government institutions continue the research on this field. In Figure 2, the global energy consumption by source and the renewables sources in detail can be seen. The use of renewable sources is continuously growing, especially in Europe.. SOURCE: (Urban, 2015) Figure 2: Total world energy consumption by source. 2.1.1.1 Increasing energy demand The energy needs of most of the developed countries in the western world are increasing at a modest level. However, in underdeveloped countries, where the economy is.

(18) 6. booming, energy demands are increasing dramatically, e.g., in China and India. If many of the third world countries were to dramatically increase their standard of living, there are estimates that worldwide energy consumption would double (International Energy Agency, 2017). The main problem is the energy sources available to produce all this energy: petroleum cannot supply it all and neither can natural gas or coal. Therefore, a development of new renewable energy sources is needed. In Figure 3 the world energy consumption until 2012 and the energy projections by source until 2040 are presented.. SOURCE: (EIA, Independent Statistics & Analysis, 2013) Figure 3: World energy consumption by source, 1990-2040 expressed in quadrillion British Thermal unit (Btu). 2.1.1.2 Dependence on foreign fuel sources Spain and in general the EU are highly dependent on crude oil to produce fuels for transportation. Figure 4 shows the global energy demand by sector. The transportation sector is almost all oil based and the EU is basically a consumer, depending on foreign sources of oil, due to the low local production..

(19) 7. SOURCE: (BP, 2015) Figure 4: Global energy demand by sector expressed in billion tons of oil equivalent (toe). The main countries that export oil for the EU are Russia, Norway and Nigeria, as it can be seen in Figure 5.. SOURCE: (European Commission, 2017) Figure 5: EU Oil Importers 2014: The top then by market share. In recent years, petroleum became less available and more expensive, and the replacement by alternative fuels emerged because their economy was becoming more favorable. However, due to lower demand and high petroleum supply and to the development of fracking, prices drastically dropped, affecting the growth of alternative fuels. There is one factor that will most likely reverse this trend: energy demands will continue to increase worldwide. For future transportation fuel needs, most likely improvements in liquid fuels will be necessary..

(20) 8. Regarding all the problems in many of the main oil producers countries as well as the problems in international relationships between these countries and the EU and the volatile oil prices that can affect the economic stability of the EU, it would be interesting to continue developing renewable fuels with materials that are already available in the EU, like biofuel from grapeseed oil and wine rests, as presented in this project. 2.1.1.3 Reduction of GHG emissions There is scientific consensus that GHG production is increasing, which has led to climate change and several other environmental concerns. Much of the severe weather that has been occurring worldwide is due to climate change issues. There is a significant amount of evidence to substantiate the existence of climate change and overall warming of the earth. The change in climate is due to the Greenhouse Effect; it is a natural effect, caused by CO2 and water vapor naturally present in atmosphere. In Figure 6 a graphic where CO2 levels are plotted regarding changes in average global temperatures from 1880 to 2010 is presented. The change has been most dramatic in the last 30 years.. Figure 6: Plot of global temperature and CO2 concentration from 1880-2010. SOURCE National Oceanic and Atmospheric Administration (NOAA)/ Global Climate Change Indicator https://www.ncdc.noaa.gov/monitoring-references/faq/indicators.php.

(21) 9. Another problem could stem from increased production of natural gas, which consists primarily of methane. Sources include petroleum and natural gas production systems, landfills, coal mining, animal manure, and fermentation of natural systems. Methane has 25 times the global warming potential of CO2. The use of biofuels could have great potential for reducing the impact of CO2 and CH4, if done well. However, some actions in South America have shown that if the switch to biofuel growth is not handled well, a greater problem can be created. Some rainforest areas were removed from South America to clear land for producing biofuels, but the rainforests that were removed were burned, putting an excessive amount of CO2 in the atmosphere. Due to this change on the land use and regarding the European legislation (European Commission, 2009), the fuels produced with the energy crops planted in these areas would not be considered biofuels. 2.1.2 SUSTAINABLE DEVELOPMENT Achieving ‘sustainable development’ requires methods and tools to help quantify and compare the environmental impacts of providing goods and services (‘products’) to our societies. These products are created and used because they fulfil a need, be it an actual or a perceived one. Every product has a ‘life,’ starting with the design/development of the product, followed by resource extraction, production (production of materials, as well as manufacturing/provision of the product), use/consumption, and finally end-oflife activities (collection/sorting, reuse, recycling, waste disposal). All activities, or processes, in a product’s life result in environmental impacts due to consumption of resources, emissions of substances into the natural environment, and other environmental exchanges (e.g., radiation) (Rebitzer, 2004). Figure 7 presents a simplified scheme of the product life concept, which is usually referred to as a ‘life cycle’, as it includes loops between the several life phases..

(22) 10. Figure 7: Schematic representation of a generic life cycle of a product SOURCE: (Rebitzer, 2004). 2.1.2.1 The life cycle assessment as a sustainability tool Life-Cycle Assessment (LCA) is a process to evaluate the environmental burdens associated with a product, process or activity by identifying and quantifying energy, materials used, wastes and emissions released into the environment; to assess the impact of those energy and material uses and releases to the environment; and to identify and evaluate opportunities to affect environmental improvements. The assessment includes the entire life-cycle of the product, process or activity, encompassing extracting and processing raw materials; manufacturing; transportation and distribution; use; re-use; maintenance; recycling, and final disposal (Consoli, 1993). The LCA was developed from the 70’s to the 90’s. During this period, environmental issues like resource and energy efficiency, pollution control, and solid waste became issues of broad public concern. From 1990 until 2000 the LCA directives were given by the Society of Environmental Toxicology and Chemistry (SETAC) and then they were standardized by the International Organization for Standardization (ISO), which adopted the formal task of standardization of methods and procedures..

(23) 11. Nowadays, the attention to LCA has increased even more due to the continued importance in European Policy and to global agreements like the Paris Climate Agreement of 2015, where representatives of 196 parties dealt with GHG emissions mitigation, adaptation and finance starting in the year 2020. 191 of them signed the agreement. One of the categories analyzed in the LCA is based on carbon footprint, constituting the basis for GHG emissions calculations and making necessary to translate the functional units of LCA in order to make comparisons feasible. Regarding the need of standardizing not only the process, but also the approaches, system boundaries and allocation methods of the LCA, the European Commission created the Coordination Action for innovation in Life Cycle Analysis for Sustainability (CALCAS) in 2016 to structure the varying field of LCA approaches and to define research lines and programs to further LCA (Guinée, 2011). 2.2 WINE AND GRAPESEED OIL PRODUCTION 2.2.1 WINE PRODUCTION IN SPAIN AND THE EUROPEAN UNION Spain has a big grape variety, which makes interesting to analyze the potential of using the wine rests to produce biodiesel. Our country has almost 1 Mha vineyards, making Spain the country with the biggest extension of vineyards in the world. Half of these vineyards are localized in Castilla-La Mancha, with almost 45 % of the total of vineyards (ICEX, 2014), as it can be seen in Table 1. The other 55 % is mainly situated in Castilla y León, Extremadura and Comunidad Valenciana. La Rioja is one of the most important wine production regions, even though the only have 4.75 % of the total of vineyards; they have one of the worldwide most important Denominations of Origin. This is due to the high quality of its grapes and the wines that are produced there..

(24) 12 Table 1: Area currently planted with vineyards in Spain, detailed by regions. Area actually planted (ha) Region. wine with Protected Designation of Origin (PDO)(*)(2). wine with Protected Geographic Indication (PGI)(**), of which are included in wine with PDO (3). wine with Protected Geographic Indication (PGI)(**), of which are not included in wine with PDO (4). (1) ANDALUCÍA ARAGÓN ASTURIAS BALEARES CANARIAS CANTABRIA CASTILLA LA MANCHA CASTILLA Y LEÓN CATALUÑA EXTREMADURA GALICIA MADRID MURCIA NAVARRA PAÍS VASCO LA RIOJA C. VALENCIANA. (2). (3). (4). 24 133.00. 2 502.00. 26 635.00. 29 280.00. 5 413.00. 104.00. Total of all regions. wine without PDO/PGI and situated outside of a PDO/PGI area (5). total. (5). (6). 2 864.00. 312.00. 29 811.00. 34 693.00. 1 774.00. 890.00. 37 357.00. 0.00. 104.00. 0.00. 0.00. 104.00. 1 466.00. 335.00. 1 801.00. 130.00. 0.00. 1 931.00. 6 215.00. 0.00. 6 215.00. 12 592.00. 0.00. 18 807.00. 0,00. 117.00. 117.00. 0.00. 2.00. 119.00. 437 642.00. 12 599.00. 450 241.00. 0.00. 0.00. 450 241.00. 66 42.,00. 8 908.00. 75 335.00. 0.00. 0.00. 75 335.00. 52 676.00. 0.00. 52 676.00. 2 523.00. 1 180.00. 56 379.00. 34 536.00. 31 894.00. 66 430.00. 11 001.00. 0.00. 77 431.00. 20 947.00. 2 521.00. 23 468.00. 0.00. 9 901.00. 33 369.00. 12 327.00. 0.00. 12 327.00. 0.00. 1 775.00. 14 102.00. 19 064.00. 0.00. 19 064.00. 0.00. 5 481.00. 24 545.00. 18 304.00. 22.00. 18 326.00. 15.00. 117.00. 18 458.00. 14 116.00. 0.00. 14 116.00. 0.00. 0.00. 14 116.00. 46 379.00. 181.00. 46 560.00. 0.00. 0.00. 46 560.00. 57 620.00. 0.00. 57 620.00. 2 160.00. 251.00. 60 031.00. 841 236.00. 64 492.00. 905 728.00. 33 059.00. 19 909.00. 958 696.00. wine without PDO/PGI and situated in a PDO/PGI area (5). SOURCE: (Common Agricultural Policy, European Wine Sector, 2015). According to the Instituto de Comercio Exterior (ICEX), 51.1 % of the Spanish wines produced in 2015 were red and rose wines, while the remainig 48.9 % of the total production was white wine (ICEX, Instituto de Comercio exterior, 2015). In the EU, there are almost 3.2 Mha of vineyards, being Spain (0.96 Mha), France (0.8 Mha) and Italy (0.64 Mha) the Member States with the biggest planted areas. After these three countries, Portugal has 0.201 Mha vineyards and Romania 0.182 Mha. Regarding this, it can be stated that the plantation of vineyards is highly concentrated in the three first mentioned countries, being the wine sector an important contribution to these economies. All these data can be seen in detail in Table 2..

(25) 13 Table 2: Area currently planted with vineyards in the EU, detailed by country. Area actually planted (ha). Region. (1) BG (Bulgaria) CZ (Czech Republic) DE (Germany) EL (Greece) ES (Spain) FR (France) IT (Italy) CY (Cyprus) LU (Luxembourg) HR (Croatia) HU (Hungary) MT (Malta) AT (Austria) PT (Portugal) RO (Romania) SI (Slovenia) SK (Slovakia). wine with Protected Designation of Origin (PDO)(*)(2). wine with Protected Geographic Indication (PGI)(**), of which are included in wine with PDO (3). wine with Protected Geographic Indication (PGI)(**), of which are not included in wine with PDO (4). (2). (3). (4). 15 355.00. 21 432.00. 36 787.00. 0.00. 0.0. 102 819.39. wine without PDO/PGI and situated in a PDO/PGI area (5). wine without PDO/PGI and situated outside of a PDO/PGI area (5). total. (5). (6). 0.00. 23 201.00. 59 988.00. 0.00. 0.00. 0.00. 0.00. 38 68. 102 858.07. 0.00. 0.10. 102 858.17. 14 782.78. 33 236.45. 48 019.23. 8 657.46. 7 336.22. 64 012.91. 841 236.00. 64 492.00. 905 728.00. 33 059.00. 19 909.00. 958 696.00. 514.003,00. 195 374.00. 709 377.00. 96 393.00. 10.00. 805 780.00. 334 418.83. 155 940.75. 490 359.58. 0.00. 147 274.53. 637 634.11. 5 277.49. 2 869.47. 8 146.96. 0.00. 0.00. 8 146.96. 0.00. 0.00. 0.00. 0.00. 0.00. 0.00. 18 990.72. 0.00. 18 990.72. 2 319.34. 0.00. 21 310.06. 53 480.06. 9 506.78. 62 986.84. 1 813.26. 0.00. 64 800.10. 0.00. 0.00. 0.00. 0.00. 0.00. 0.00. 47 255.22. 0.00. 47 255.22. 0.00. 0.00. 47 255.22. 78 831.21. 25 045.18. 103 876.39. 97 568.27. 0.00. 201 444.66. 86 276.22. 27 255.13. 113 531.35. 3 062.56. 65 780.85. 182 374.76. 15 528.00. 0.00. 15 528.00. 0.00. 141.00. 15 669.00. 17 578.00. 0.00. 17 578.00. 859.00. 0.00. 18 437.00. 2 145 832 535 190 2 681 022 243 732 263 653 SOURCE: (Common Agricultural Policy, European Wine Sector, 2015). Total of all Member States. 3 188 407. Regarding the production, Italy is the country with the biggest wine production in the world with 49.5 MhL in 2015 (17.43 % of the world production). France and Spain follow with 47.5 MhL and 37.2 MhL produced, respectively (16.73 % and 13.1 % of the world production) (The Wine Institute, 2016). The difference between the amount of vineyards and the production of wine is due to European restrictions, which are detailed in Section 2.2.1.1. The main consumers in 2015 were USA, France and Italy, consuming 33 ML, 27.2 ML and 20.5 ML, respectively (13.43 %, 11.01 % and 8.3 % of the world consumption). Spain is in eighth position with a consumption of 1 ML (4.05 % of the world consumption) (The Wine Institute, 2016)..

(26) 14. The main wine markets (UK, USA, Germany, Canada, China, Japan, Belgium, Switzerland, The Nederland, Russia, France, Sweden and Denmark) purchased 7 506.9 ML and 20 564.1 M€ in June 2015 and represented 77 % of the world purchases. The Spanish world exports grew reaching 10 337 ML and 26 924 M€ in 2015 (OeMV, Observatorio Español del Mercado del Vino, 2015). European bottled wines are more frequently positioned in the higher price segments (Ultra Premium and Top Range) in third-country markets, whereas they are positioned in the lower price ranges in Germany and in the Medium Range in Denmark and UK. Wine producing Member States adopt different positioning strategies, with France consistently recording the highest prices (bottles and bulk) and Spain recording among the lowest, further decreasing for bottled wine exports in the years following the wine Common Market Organization (CMO) reform. Expected growth of wine consumption, decline of vineyard areas and wine production in the EU as well as the increase for all competitors is likely to lead to further decrease of EU wine market shares. On the other hand, restructuring and conversion of vineyards (within the reformed wine CMO), stimulates recovery of EU wines competitiveness. Low wine export propensity makes the EU less aggressive on export markets compared to its main competitors (in particular, Chile, New Zealand, Australia, South Africa and Argentina). However, a more balanced distribution of EU exports on a larger number of markets makes the EU less dependent from few vital markets (COGEA S.R.L., 2014). In order to improve the competitiveness of EU wines, a better access to the wine market should be improved by reducing the risks associated with sudden economic and political changes, by improving the expansion strategies like competitors such as Chile and Australia and by accessing better distribution channels. The product should also be adapted to the particular markets, developing a better comprehension of potential clients (OeMV, Observatorio Español del Mercado del Vino, 2015). 2.2.1.1 European regulations The EU developed a specific wine regulation in 2009 (European Commission, 2009) regarding aspects such as production control, labelling and transport. The following articles (10) and (22) state the harvest declarations that producers have to make so the EU is able to monitor the wine market..

(27) 15. (10) Article 111 of Regulation (EC) No 479/2008 states that producers of grapes intended for winemaking and producers of must and wine must make harvest declarations each year in respect of the most recent harvest and that producers of wine and must and commercial operators other than retailers must declare their stocks each year. That Article also stipulates that the Member States may also require grape merchants to declare the quantities of grapes marketed. (22) Certain information must be available on the wine market to ensure that it can be monitored. In addition to the data provided in the summaries of the various declarations, information on wine supplies, utilization and prices is essential. The Member States should therefore be required to gather this information and send it to the Commission on certain fixed dates. The EU also created a reform of the wine market in 2008 to make the EU wine producers even more competitive by enhancing the reputation of European wines and by regaining market share both in the EU and outside (Council Regulation, European Commission, 2008). Other goals of the reform were to make the market-management rules simpler, clearer and more effective, in order to achieve a better balance between supply and demand, and to preserve the best traditions of European wine growing and boosting its social and environmental role in rural areas. To achieve that, national support programs were launched to promote and enhance wine making in the mentioned areas (Meloni, 2012). Other measures such as promotion in third countries, restructuring and conversion of vineyards, green harvesting, mutual funds, harvest insurance, investments and byproduct distillation were also introduced by the 2008 Wine CMO reform (European Comisision, 2017). This was a controversial reform, due to the voluntary program of uprooting of vineyards. The EU wanted that 175 000 ha of vineyards in less competitive areas were abandoned in three years from 2009. The uprooting was subsidized and once the vineyards were uprooted, the land could not be planted again with them due to the restrictions of the EU regarding vineyards and plantation areas. Wine making and labeling rules were also introduced by this reform..

(28) 16. Another reform is in force since 2013 (European Commission, 2013), introducing new innovation measures aiming the development of new products, processes and technologies concerning the wine products. Furthermore, it opens promotion measures to information in Member States, with a view to informing consumers about the responsible consumption of wine and about the Union systems covering designations of origin and geographical indications. It also extends the restructuring and conversion of vineyards to replanting of vineyards where that is necessary following mandatory grubbing up for health or phytosanitary reasons. Nowadays, the average density of plantation for vineyards in Spain is of 3 000 grapevines by hectare (ha). The plantation density is the number of grapevines planted in a hectare (10 000 m2) (Viveros Barber). This is also regulated by the EU, being the minimum density 2 850 grapevines by hectare and 4 000 the maximum. 2.2.2 WINEMAKING The winemaking process begins by preparing the field for the vineyards plantation. First, the field has to be cleaned of vegetable rest and stones and worked in a depth of approximately 40-80 cm to move the soil and facilitate plants growth. The desired grapevine variety has to be selected and the field has to be mapped to calculate how many vineyards are needed and the optimal distance between them. The distances have to be marked in the field, taking into account the needed spaces for machinery and service ways. The holes are filled with the seeds, covered with fresh soil and watered. It is very important to verify that the roots are humid. In spring, fertilizers have to be added (approximately 5 g per plant diluted in 10 L of water) to the plant by watering them regularly during the spring and the summer. It is very important to maintain the field clean and without weed. The vineyards have to be observed regularly in order to detect spots in the leaves, bugs or other plagues. They also have to be pruned when needed to guarantee a correct growth. Once the grapes are ready, they have to be harvested and the winemaking process can start..

(29) 17. In the following, the wine elaboration process will be explained. The process is addressed to red wine, since it is the mainly produced in Spain (MAPAMA, 2016). However, even though the elaboration of white wine presents some differences, the grapeseed extraction is performed in the same way. 1. Grape Harvest: When the grape has reached its optimum maturation point, it is harvested with trailers carrying boxes or small baskets that do not exceed 25 kg of capacity. The transport should avoid the warming of the grapes. The harvest moment depends on the grape type, the region, the climatic conditions of the specific year and the type of wine being produced. Once the grapes are in the factory, a sample is taken, weighed and analyzed to determinate the sanitary status and the sugar content of the grape. 2. Mechanical treatment: Elaboration of the wine in the factory, that consist of the following steps: a. De-stemming: The stem that holds the grape bunch together has to be removed. To do that, a rotating cylinder with holes, called destemmer, is used. The grapes fit into the holes and fall while the stem stays and is later removed. In Figure 8, this machine can be seen.. SOURCE: Destemmer Zambelli Traminer, STM-1200, http://distillersvault.com/index.php?p=view_product&product_id=4116 Figure 8: Destemmer.

(30) 18. b. Pressing: By pressing, the pomace of the grape bunch is broken and the grapeseed are separated in order to obtain the must. This is an important step because the solid part (pomace and grapeseed) is separated from the liquid part (must). These two parts (solid and liquid) have to be in contact in the next process, as it would be explained later. The grapeseed should not break because otherwise they could make the wine bitter. Therefore, the pressing should not be very hard. c. Fermentation and maceration: Two simultaneous processes are carried out while the must is still in contact with the pomace and the seeds: the fermentation and the maceration. The first one is carried out by yeasts, which transform the sugar of the must in alcohol. In the second one, due to the contact of the solid parts with the liquid, the future wine will obtain color and tannins. Tannins are polyphenolic biomolecules that precipitate proteins and other organic compounds like amino acids and alkaloids. This process lasts 10 to 14 days at a temperature of 29 ºC and is an exothermic process. Because of the yeasts that carry out the process, the control of the temperature is very important in this period. It represents the main energy consumption of the process due to the cooling and temperature control systems. To minimize this consumption, the temperature should be controlled to be as high as possible, so the refrigeration is as low as possible. At the end of this process the solid part, which contains the pomace and the grapeseed, is removed. The pomace forms grape liqueur and the seeds are either also dedicated to produce grape liqueur, or maintained humid and relatively soft in order to be later used to produced grapeseed oil. It is important for the grapeseed oil production process that the seeds do not get dry so a cake from which the oil would be later extracted can be produced. This process will be later explained in 2.2.3.1. d. Malolactic fermentation: During this process the wine is de-acidified by converting the malic acid into lactic acid. The microbiological process.

(31) 19. takes place thanks to the lactic bacteria that are naturally present in the grape. The malolactic fermentation lasts between 15 and 21 days at temperatures of 20-23 ºC. e. Decanting and filtration: The solid substances like yeasts that are accumulated at the end of the deposits and barrels are removed. f. Barrel aging: After the process, the wine is introduced into the barrel in a fresh and dark place to age and mature. The temperature is controlled and has to be between 10 and 18 ºC, while the humidity has to be 60-80 %. Depending on the barrel aging time, Spanish wines can be classified into ‘young’ (1-2 years aging), ‘crianza’ (1 year aging in oak and 1 year in bottle), ‘reserva’ (1 year aging in oak and 2 years in bottle) or ‘gran reserva’ (2 years aging in oak and 3 years in bottle). g. Tartaric stabilization: Crystals are formed in the wine and even though they do not affect the flavor, their presence annoys the client, due to the solid formations in the liquid. Therefore, they are removed, which results in an important energetic consumption due to refrigeration. This energy consumption could be reduced by 90 % by using electro-dialysis. h. Bottling: Once these processes are concluded, the wine is bottled to finish its preparation. In the bottle it will reach the final and optimal consumption time (Comfort, 2008) (ICEX E. e.). 2.2.3 GRAPESEED OIL PRODUCTION Grapeseed oil is a product resulting from the processing of grape. It is appealing for the cosmetic and pharmaceutical industries because of its antioxidant properties that are due to the large content of unsaturated fatty acids. Still, in the transformation of the must into wine, grapeseeds are a leftover in its majority. Therefore, they can be used to produce grapeseed oil, which can be transformed by transesterification into biodiesel. Regarding the whole process while analyzing this biodiesel, not only the energy market and its characteristics have to be taken into account, but also the agricultural market. Using grapeseed oil as a precursor for energy in form of biodiesel can create employment and contribute to the industrial development in rural areas. The consequent.

(32) 20. energy production and usage would be sustainable, especially if the demand is geographically correlated with the offer and the production. The efficiency of the agricultural market does not get affected by considering grapeseed a byproduct instead of a disposal. The main use of the grapeseed is oil and grape liqueur production. The first one is used as a cosmetic or as a gourmet gastronomic product, while the second one is an alcoholic beverage produced by distillation of grape pomace. Grape pomace is composed by solid disposals of wine production and is a mix of stems, pulp and seeds in variable quantities (in average 25 %, 55 % and 20 %, respectively). However, the demand of these products does not cover the high production of grapeseed annually, so millions of tons of grapeseed are discarded each year. This enhances the interest of producing biodiesel from this raw material (Gutiérrez de la Llave, 2016); (FEDNA). 2.2.3.1 Grapeseed oil extraction In Figure 9 the common extraction process of vegetable oils is presented. This can also be applied for grapeseed oil extraction. First, the oil seeds have to be cleaned and the hulls have to be removed. Once the kernels are separated, they are crushed and preheated to extract the water content from the pulp that has formed. After that, they are either pressed to form a cake or a solvent extraction is performed. Oil press has weak oil yield and high impurity and broken unsaturated fatty acid are formed during high temperature extraction process. In order to perform the oil extraction, a vibrating screen removes impurities of grapeseed raw material like peels. After that, the conveyor sends cleared material into the softening pot, which has a temperature between 65-80 ℃ after adding water and the material stays there for about 15 min for further soften. Then, irons are removed and sent to embryo flaking machine to get a 0.3 mm, with 8 % of moisture content, cake. This is later sent to grapeseed oil extracting plant..

(33) 21. Figure 9: Common extraction process of grapeseed oil. 2.3. BIODIESEL According to the American Society for Testing and Material (ASTM), biodiesel is described as methyl or ethyl esters of long chain fatty acids derived from lipids such as vegetable oils or animal fats , which have their main use in compression engines. The biodiesel is produced through transesterification: an exchange process between the organic group R of an ester and the organic group R’ of an alcohol. The reaction is usually catalyzed by an acid, a base or a biocatalyst (enzymes). The main goal of the transesterification process in the production of biodiesel is to reduce the viscosity of the vegetable oil. 2.3.1 CLASSIFICATION OF BIODIESEL One of the possible classifications of biodiesel is according to generations; taking into account the technological advance degree by means of production and utilization. . First-generation: Includes biofuels that are made from sugar, starch, vegetable oil, or animal fats using conventional technology (transesterification). These are generally produced from grains with a high sugar content that are fermented into bioethanol or seeds that are pressed into vegetable oil. Some common biofuels of this category are vegetable oils, biodiesel, bio-alcohols, biogas, solid biofuels and syngas.. . Second generation: This category includes biofuels that are produced from non-food crops, such as cellulosic biofuels and waste biomass. The crops are cultivated in.

(34) 22. non-agricultural land. Examples of this category are the same as the ones from first generation, regarding that the raw materials are non-food crops. Also bio-hydrogen, bio-methanol, DMF, Bio-DME, Fischer-Tropsch diesel, bio-hydrogen diesel, mixed alcohols and wood diesel belong to this category. . Third generation: Includes biofuels that are produced from extracting oil of algae, bacteria and fungi using developing technologies. Its production is supposed to be low cost and high-yielding (producing 30 times the energy per unit area as can be realized from current, conventional ‘first-generation’ biofuel feedstocks). However, the technologies used for this meaning are still in development and its aim is to reach similar compositions as the vegetable oils used in first- and second-generation fuels. 2.3.2 PRODUCTION OF BIODIESEL 2.3.2.1 Biodiesel market trends. The production of biodiesel has been increased globally in the last years due to government’s promotions and subsidies, the increase of the oil price and the also raising social awareness regarding the climate change and the environment care. This can be seen in Table 3, where the increase in global production of biodiesel is plotted. The production has tripled from 2004 until 2013, where the increase stops being exponential and begins to be slower until 2015, where there was a decrease in the production. Table 3: Biodiesel global production from 2004 to 2015. 35. Global production of biodiesel. Millons tons/year. 30 22.31. 25 20. 14.49. 15 10 05. 5.92. 16.72. 24.19. 27.06. 29.25 25.5. 19.04. 8.63. 1.97 2.96. 00 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015. SOURCE: Oil World Static Update & Energy Information Administration https://www.eia.gov/outlooks/steo/report/global_oil.cfm.

(35) 23. This decrease was originated by the decrease of the oil prices in 2008. The biodiesel production is linked to the prices of the fossil fuels, so when fossil fuels have a lower price, the investments in new technologies like biodiesel are reduced, too. Therefore, due to the low price of the oil, the production of biodiesel started to be non-profitable. The subsidies for biodiesel vary from country to country, being the Brazilian government one of the ones that has invested the most. It supports a 30 year old ethanol program in which is mandatory to blend anhydrous ethanol (in a 25 % nowadays) with gasoline. USA developed an Energy Policy Act in 2005 in order to generate 7.5 billion USA gallons by 2012 and an Energy Independence and Security Act in 2007 to generate 36 billion USA gallons by 2022. The EU developed a Directive 2003/30/EC in May of 2003 with the goal of having 5.75 % share of renewable energy in the transport sector by 2010. However, the blending targets were not achieved, with 4.26 % share in 2010. Later, another Directive (Directive 2009/28/EC) was release in April of 2009 regarding the promotion of the use of energy from renewable sources. The EU’s renewable energy directive sets a binding target of 20 % of final energy consumption from renewable sources by 2020 (The European Parliament and the Council of the European Union, 2009). Each country had a different political motivation to biofuel promotion: in a simplified point of view, Brazil wants to use cheap and locally available energy, the USA wants to use it to give subsidies to the agriculture and to achieve energy security, while the EU wants to reduce the Greenhouse Emissions (Pitsch, 2016). All this data can be seen in Figure 10.. Figure 10: Regional production of ethanol and biodiesel in 2011 as a percentage of global production SOURCE: (Renewable Energy Network, 2016).

(36) 24. In Figure 11, the increase of ethanol production in the USA can be seen. This is principally due to the increase of the bioethanol production.. Figure 11: Ethanol production in the USA SOURCE: (RFA, Renewable Fuels Association). In the EU the consumption of biofuel (liquid and biogas) for transport has also increased over the last 13 years, with a slight decrease in 2015. The countries that consume the biggest amount of biofuels are France with a total consumption in 2015 of 2.996 Mtoe, Germany with 2.578 Mtoe and Italy with 1.153 Mtoe. Spain is the fifth country in the consumption of 0.970 Mtoe. in 2015, with 0.181 Mtoe. of bioethanol and 0.788 Mtoe. of biodiesel (Eurobserver, 2015). Biodiesel is almost completely sold as fuel mixture and the direct sales at gas stations are insignificant. As it can be seen in Table 4, the total sales of biodiesel were 13 899 ML in 2015 in the EU..

(37) 25 Table 4: EU Biodiesel Consumption (Million liters). e= estimate / f= forecast EU FAS Posts SOURCE: (Flach B. L., 2016). 2.3.2.2 Steps in the biodiesel production Biofuels mainly come from the grain of plants, making bioethanol or biodiesel. The first one is produced by fermentation of sugars from cereals, sugar cane and beet, while the second one is formed by methyl or ethyl esters that are produced by vegetable oils or animal fat. In the following Figure 13, the specific processes for the conversion of bioethanol and biodiesel are detailed.. SOURCE: (Pitsch, 2016) Figure 12: Conversion processes of biofuels. This project focus on biodiesel produced from grapeseed oil and wine excess. The grapeseed oil has to be processed via transesterification to obtain the biodiesel due to.

(38) 26. the high viscosity of vegetable oils. This high viscosity implies high flow resistance of the fuel which causes the injection systems to work outside of specifications.. SOURCE: (Pitsch, 2016) Figure 13: Production process of biodiesel. The following steps, which can be seen in Figure 15, are needed in the production of biodiesel from vegetable oil: 1. Mixing of triglycerides, ethanol and catalyst (typically NaOH, KOH which is dissolved in alcohol). 2. Transesterification at process conditions of T = 50 –65 °C and p = 1 atm. 3. Heavy mixture of glycerin, ethanol and ethanolate settles at the bottom of the reactor and is drawn off. Both glycerin and biodiesel need to have alcohol removed and recycled in the process. 4. Surplus ethanol is separated from both phases (distillation, flash evaporation) and reused..

(39) 27. 5. Products (FAEE and glycerin) are washed in a different column. Water is added to both the biodiesel and glycerol to remove unwanted side products, particularly glycerol, that may remain in the biodiesel. The wash water is separated out similar to solvent extraction (it contains some glycerol), and the trace water is evaporated out of the biodiesel. Acid is added to the glycerol in order to provide neutralized glycerol (Pitsch, 2016). Transesterification process Transesterification is the conversion of a carboxylic acid ester into a different carboxylic acid ester. The biodiesel is produced mainly through transesterification transforming the vegetable oil into biodiesel. First, a mixture of the alcohol for the reaction with the catalyst, which is typically a strong base such as NaOH or KOH, is made. The mixture reacts then with the fatty acid so that the transesterification reaction takes place as shown in Figure 16.. Figure 14: Transesterification reaction of a vegetable oil with an alcohol. The catalyst is prepared by mixing an alcohol and a strong base such as NaOH or KOH. The alcohol should be as dry as possible in order to avoid water formation, which could enhance the possibility of soap formation. The use of the catalyst reduces the reaction time (Clifford, 2015). Once the catalyst is prepared, one mol of triglyceride will react with 3 moles of alcohol, so excess alcohol has to be used in the reaction to ensure complete reaction. The three attached carbons with hydrogen react with OH- ions and form glycerin, while the CH3 group reacts with the three fatty acid moles to form the fatty acid ester (Clifford, 2015)..

(40) 28. The transesterification is a reversible reaction, so in order to drive the reaction to the product side, excess alcohol has to be used. The amount of this excess alcohol, as well as the catalyst concentration, have to be added regarding the temperature and reaction time, which may vary and have to be experimentally determinate for each type of oil. Alcohol for transesterification: Methanol or Ethanol The bioethanol production from biomass can be seen in Figure 14 where the different process and compounds of each part of the conversion are detailed. In this case, fermentation and distillation are the methods used to form bioethanol, which can be used directly as biofuel or in the transesterification process to form FAEE.. SOURCE: (Sivakumar, 2010) Figure 15: Possible pathways for bioethanol fermentation from cellulosic feedstock. In this project, the alcohol used would be ethanol, forming FAEE, since it allows a more renewable fuel production. The ethanol considered in this project would come from the distillation of wine surpluses..

(41) 29. On the contrary, the methanol is mainly produced from syngas from fossil resources and is highly toxic. Synthesis gas is a gas mixture of hydrogen and carbon monoxide and it is the fossil resource that is mostly used. The production of methanol usually consists of three basic steps independent of the feedstock material: synthesis gas preparation, methanol synthesis and methanol purification. The mentioned synthesis consists mainly of the following equations: CO + 2H2 ⇌ CH3OH CO2 + 3H2 ⇌ CH3OH + H2O CO2 + H2 ⇌ CO+H2O All three equations are reversible and thus the process conditions regarding temperature, pressure and synthesis gas mixture are important to control. The first two equations are exothermic, so the processes produce heat and require cooling. Some heat is normally recovered and used for other parts of the synthesis. Other processes like Carnol process, Bi-reforming and direct oxidation of methane to methanol are being developed as attractive alternative for synthesis of natural gas to methanol in order to reduce the CO2 emissions and the energy consumption. 2.3.3 ADVANTAGES AND DISADVANTAGES OF BIODIESEL The main advantages of biofuels are: 1. Fewer emissions in burning are created: Biofuels are cleaner fuels in comparison with gasoline and diesel, and therefore produce fewer emissions on burning. This affects the performance of the engine, allowing them to run longer while requiring less maintenance. It also reduces the overall pollution costs, so in the future this factor and the increasing demand will allow the biofuels to be produced under cheaper costs. Also, the use of biofuels does not require a lot of modifications in the engine so the transition from fossil fuels to biofuels could be easily done regarding this aspect. 2. Diversification of the agricultural production: Biofuels can be made from many different sources such as manure, waste from crops and energy crops. This.

(42) 30. allows the usage of local raw material to produce biofuels as well as the use of agricultural disposals. Also, crops which are not suitable for its consumption as food, such as Jatropha curcas, could be used. 3. Reduction of dependence of foreign oil: By using local raw materials to produce biofuels, local employment can be created and the dependence of foreign oil can be reduced. This contributes to energy independence of countries and economic security. 4. Recyclable energy: Biofuels are a renewable energy, as they use renewable sources and even wastes or agricultural disposal that would not be useful otherwise. 5. Reduction of the CO2 footprint and greenhouse emissions: Since biofuels are made of renewable raw materials, they generally cause less pollution to the planet in comparison with diesel or gasoline. Normally, the levels of CO2 and sulfur are lower than the ones of the mentioned fuels. Nevertheless, the whole life cycle has to take into account, including the byproducts and transport emissions, which could increase significantly the total emissions of the biofuel. Anyway, the greenhouses gases that are produced while burning biofuels are lower than the ones from diesel and gasoline and their usage reduce the impact on the ozone layer. Also, in the case of biofuels, the CO2 that is released to the atmosphere during the combustion is not considered as an emission since it is equivalent to the CO2 that was captured by the plant during its growth. 6. Improvement of crops efficiency: By using agricultural disposals, pruning rests and other derivatives of crops, the efficiency can be increased, as the volume of material that is being used for consumption (energy, food and other uses) increases. The main disadvantages of biofuels are: 1. High cost of production: Its production is only viable with subsidies due to the high costs that nowadays double the fossil fuel costs. 2. Monoculture: Monoculture refers to the production of the same crops every year, rather than producing various crops through a farmer’s fields over time..

(43) 31. This might be economically attractive, but it may deprive the soil of nutrients and can make the fields less efficient or even barren. 3. Crystal formation at low temperatures: Unlike diesel, biofuels can solidify and form crystals that can block the fuel channels. This requires a very good monitoring and stabilization of parameters that can affect the temperature. 4. Use of fertilizers: Crops need fertilizers to grow better and avoid plagues, but they can have harmful effects on surrounding environment and may cause water pollution due to its nitrogen and phosphorus levels. 5. Biofuels can cause deforestation: In sensible zones and if the crop is not harvested regarding sustainability criteria, deforestation of the zone can follow. The usage of crops that can be used as food crops has to be controlled, due to the limited agricultural space. This can create problems in the long term such as shortage of food and rise in food prices. 6. Industrial pollution: The whole production of biofuels has to be taken into account under the performance of a Life Cycle Assessment. That way, all the inputs and outputs of the manufacture can be included into the carbon footprint calculation. Large scale production of biofuels can emit large amounts of emissions and required too large quantities of water to irrigate the crops. This may impose strain on local and regional water resources as well as put unsustainable pressure on them. 2.3.4 PROPERTIES OF BIODIESEL To insure quality biodiesel, there are standards tests to see that it meets use specifications. The European Council and the ISO have two methods to legally define biodiesel for use in diesel engines, labeled EN 590:2004 and EN 14214:2012. Table 5 shows the test methods necessary for all the expected standards for biodiesel, which are applied for FAME and FAEE. Table 5: Legal definition of biodiesel according to EN 590:2004 and EN 14214:2012. Property. EN ISO Method. Limits. Units. Ca and Mg combined. EN 14538. 5 max. ppm (ug/g). Flash point. EN ISO 2719. 101 min. °C.

(44) 32. Alcohol Control. -. -. -. Methanol content. EN 14110. 0.2 max. % mass. Flash point. EN ISO 2719. 101 min. °C. Water. EN ISO 12937. 500 max. mg/kg. Kinematic Viscosity, 40 °C. EN ISO 3104. 3.5-5.0. mm2/s. Sulfated Ash. ISO 3987. 0.02 max. % mass. Sulfur 10 mg/kg Grade. EN ISO 14596. 0.01 max. % mass (ppm). 50 mg/kg Grade. EN ISO 8754. 0.05 max. % mass (ppm). Copper Strip Corrosion. EN ISO 2160. Class 1. -. Cetane. EN ISO 5165. -. Cold Filter Plugging Point. EN 23015. 51 min Location and season dependent. Carbon Residue on 10 % distillation residue, max. EN ISO 10370. 0.30 % wt. % mass. Acid Number. EN 14104. 0.5 max. Mg KOH/g. Mono Glycerin Total Glycerin Phosphorus Content Distillation, 65 %. EN 14105 EN 14105 EN 14107 prEN 16294 EN ISO 3405. 0.7 max 0.20 max 4.0 max 350 max. % mass % mass mg/kg °C. Sodium/Potassium, combined. EN 14538. 5 max. ppm (ug/g). Oxidation Stability. EN 14112. 8 min. hours. °C. SOURCE: European Council and International Standards Organization. There are advantages and disadvantages of using biodiesel compared to ultra-low sulfur diesel: biodiesel has a higher lubricity, low sulfur content, and low CO2 and hydrocarbon emissions. This makes it good to blend with diesel from petroleum. However, biodiesel has poor cold weather properties and it really depends on the location, as there could be problems in the winter (Clifford, 2015). The properties of the biodiesel have to be almost the same as the ones of fossil fuels to allow the mixture of the two to use the blend in engines..

(45) 33. 2.4. LIFE CYCLE ASSESSMENT The Life Cycle Assessment (LCA) is an environmental management tool that studies the environmental aspects and the potential impacts along the life cycle of a product, process or activity. In the LCA of a product all the environmental effects derivate from the raw materials consumed and the energy needed in the manufacture are allocated to it, from its origin as raw material until its end as waste, including the emissions and wastes generated in the production process. The LCA applied to the agriculture is focused specially on the consequences for the environment for the emissions and no-renewable energy inputs used. It considers the footprint of all processes developed in a product life cycle and the impact of the extraction of the natural resource and the product disposal. Nevertheless, the final results of this analysis depend on the subjective evaluation done in each part of the assessment (Sanz Requena, 2008). 2.4.1. APPLICATIONS OF THE LCA As the LCA is a method to help quantify and evaluate the potential environmental impacts of goods and services, it can be applied to any kind of product and to any decision where the environmental impacts of the complete or part of the life cycle are of interest. As shown later in Figure 15, the main direct applications of LCA are in the development and improvement of a product, in strategic planning, in public policy making and in marketing. Additionally, LCA can be applied by different stakeholders and actors associated with the life cycle. LCA has been applied by governmental organizations, nongovernmental organizations, and industry in a wide variety of sectors, either autonomously or with the help of research institutes or consultants. The LCA can imply different advantages regarding the goals for which it has been carried out and the actors involved. Therefore, two main groups of actors have been analyzed: the industry and the public administration..

(46) 34. 2.4.1.1 LCA for the industry Regarding the industry, a distinction between a multinational corporation and Small and Medium Enterprises (SMEs) and start-ups have to be made. LCA at a multinational corporation Due to the natural size of multinational organizations, normally there are dedicated resources available to apply LCA (time, money, software tools, knowledge, databases, etc). The LCA is a useful tool and it should be linked with economic and social data regarding environmental decision making processes. One of the biggest advantages of multinational corporations regarding the Life Cycle Inventory Analysis (LCIA) is that they usually have their own data inventories for their processes and products. Their challenges are how to conduct simplification, what to focus on and how to weigh certain environmental aspects against each other. Therefore, they need to establish their own standards and these need to be flexible enough for regional and brand-specific interpretation (Rebitzer, 2004). The main applications in this sector are: . Material choices.. . Technology choices such as comparison of different propulsion systems, comfort/feature approaches, vehicle comparisons, etc.. . Product and process evaluation, target setting and benchmarking.. . Infrastructure and location choices.. LCA at SMEs and start-ups These types of enterprises are often discouraged from focusing on anything other than time to market, time to cash, and core competencies. However, carrying out LCA can be a win-win solution where both environmental improvements and economic benefits can be reaped..

(47) 35. Regarding the capital limitations, the need of careful planning and the common environmental risk evaluation which large financial institutes impose on small firms and start-ups, LCA applications, and the potential risks associated without it are more important as the size of the firm decreases. The main advantages for such enterprises of completing LCA of their products are: . Reduced operating costs via the supply chain coordination of transports to reduce the fraction of vehicles travelling with light or empty loads.. . New product introduction by considering unused raw materials as a marketable asset rather than a cost-centered waste stream.. . Improved relations with authorities and reduced disposal costs.. . Favorable image to local and regional politicians.. . Improved credit terms with major financial institutions.. . Reduced costs to certify to ISO 9001 and 14001, which also brings indirect benefits via improved stakeholder coordination.. . Reduced overhead by having in place an environmental management system.. The accumulation of the items listed also is important for the firms in the IPO (initial public offering) stage, as well as when seeking external capital (Rebitzer, 2004). 2.4.1.2 LCA for the public administration Governments are in general involved in promoting methodological developments and capacity building by sponsoring research programs and workshops, producing illustrative case studies, developing supporting tools, databases, etc. Especially in Europe, a movement promoting product-oriented environmental policy has evolved, regarding environmental labelling, the inclusion of environmental aspects in public purchasing, linking process-and plant-focused environmental management with the life cycle perspective, and making life-cycle data available. One of the European policies that promote all this aspects is the Integrated Product Policy (IPP) (European Commission, 2003)..

(48) 36. The life cycle approach was also a central theme in the EU communications related to waste prevention, recycling, and the sustainable use of resources (European Commission, 2003). In the most of the EU member states, LCA is already implemented and in a few instances, national authorities in the EU referred to the LCA stating that ‘life-cycle assessments should be completed as soon as possible to justify a clear hierarchy between reusable, recyclable and recoverable packaging’ and have been also applied to justify legislative measure to discriminate between packaging systems (Rebitzer, 2004). 2.4.2 REGULATION OF LCA The origins of LCA are studies to compare the characteristics of different products. Since then, it has developed until becoming a very useful tool regarding environmental management. The International Standards Organization (ISO) began to work on the standardization of LCA on 1994. Since then, several norms and actualizations have followed, until the development in 2006 of the current ones: . ISO 14040. Environmental management. Life Cycle Assessment. Principles and framework.. . ISO 14044. Environmental management. Life Cycle Assessment. Requirements and guidelines.. The LCA is not regulated by any legislation, though it is based on the main directives and legislations regarding environmental management systems developed by the European Union and Spanish legislation. 2.4.3 PRODUCT LIFE-CYCLE The lifecycle of a product consists on all the steps from the life of a product, from the extraction of the raw material to the final disposal. Regarding a general product, the classification of the steps could be as follows:.